Cell and tissue stiffness is an important biomechanical signalling parameter for dynamic biological processes; responsive polymeric materials conferring responsive functionality are therefore appealing for in vivo implants. We have developed thermoresponsive poly(urea-urethane) nanohybrid scaffolds with 'stiffness memory' through a versatile 3D printing-guided thermally induced phase separation (3D-TIPS) technique. 3D-TIPS, a combination of 3D printing with phase separation, allows uniform phase-separation and phase transition of the polymer solution at a large interface of network within the printed sacrificial preform, leading to the creation of full-scale scaffolds with bespoke anatomical complex geometry. A wide range of hyperelastic mechanical properties of the soft elastomer scaffolds with interconnected pores at multi-scale, controlled porosity and crystallinity have been manufactured, not previously achievable via direct printing techniques or phase-separation alone. Semi-crystalline polymeric reverse self-assembly to a ground-stated quasi-random nanophase structure, throughout a hierarchical structure of internal pores, contributes to gradual stiffness relaxation during in vitro cell culture with minimal changes to shape. This 'stiffness memory' provides initial mechanical support to surrounding tissues before gradually softening to a better mechanical match, raising hopes for personalized and biologically responsive soft tissue implants which promote human fibroblast cells growth as model and potential scaffold tissue integration. STATEMENT OF SIGNIFICANCE: Biological processes are dynamic in nature, however current medical implants are often stronger and stiffer than the surrounding tissue, with little adaptability in response to biological and physical stimuli. This work has contributed to the development of a range of thermoresponsive nanohybrid elastomer scaffolds, with tuneable stiffness and hierarchically interconnected porous structure, manufactured by a versatile indirect 3D printing technique. For the first time, stiffness memory of the scaffold was observed to be driven by phase transition and a reverse self-assembly from a semicrystalline phase to a quasi-random nanostructured rubber phase. Early insight into cell response during the stiffness relaxation of the scaffolds in vitro holds promise for personalized biologically responsive soft implants.

Nanocathodoluminescence reveals the spectral properties of individual InGaN quantum wells in high efficiency light emitting diodes. We observe a variation in the emission wavelength of each quantum well, in correlation with the Si dopant concentration in the quantum barriers. This is reproduced by band profile simulations, which reveal the reduction of the Stark shift in the quantum wells by Si doping. We demonstrate nanocathodoluminescence is a powerful technique to optimize doping in optoelectronic devices.

III-nitride core-shell nanorods are promising for the development of high efficiency light emitting diodes and novel optical devices. We reveal the nanoscale optical and structural properties of core-shell InGaN nanorods formed by combined top-down etching and regrowth to achieve non-polar sidewalls with a low density of extended defects. While the luminescence is uniform along the non-polar {1–100} sidewalls, nano-cathodoluminescence shows a sharp reduction in the luminescent intensity at the intersection of the non-polar {1–100} facets. The reduction in the luminescent intensity is accompanied by a reduction in the emission energy localised at the apex of the corners. Correlative compositional analysis reveals an increasing indium content towards the corner except at the apex itself. We propose that the observed variations in the structure and chemistry are responsible for the changes in the optical properties at the corners of the nanorods. The insights revealed by nano-cathodoluminescence will aid in the future development of higher efficiency core-shell nanorods

In semiconductor nanowires, understanding both the sources of luminescence (excitonic recombination, defects, etc.) and the distribution of luminescent centers (be they uniformly distributed, or concentrated at structural defects or at the surface) is important for synthesis and applications. We develop scanning transmission electron microscopy−cathodoluminescence (STEM-CL) measurements, allowing the structure and cathodoluminescence (CL) of single ZnO nanowires to be mapped at high resolution. Using a CL pixel resolution of 10 nm, variations of the CL spectra within such nanowires in the direction perpendicular to the nanowire growth axis are identified for the first time. By comparing the local CL spectra with the bulk photoluminescence spectra, the CL spectral features are assigned to internal and surface defect structures. Hyperspectral CL maps are deconvolved to enable characteristic spectral features to be spatially correlated with structural features within single nanowires. We have used these maps to show that the spatial distribution of these defects correlates well with regions that show an increased rate of nonradiative transitions.

The inclusion of boron within nanodiamonds to create semiconducting properties would create a new class of applications in the field of nanodiamond electronics. Theoretical studies have differed in their conclusions as to whether nm-scale NDs would support a stable substitutional boron state, or whether such a state would be unstable, with boron instead aggregating or attaching to edge structures. In the present study detonation-derived NDs with purposefully added boron during the detonation process have been studied with a wide range of experimental techniques. The DNDs are of ~4 nm in size, and have been studied with CL, PL, Raman and IR spectroscopies, AFM and HR-TEM and electrically measured with impedance spectroscopy; it is apparent that the B-DNDs studied here do indeed support substitutional boron species and hence will be acting as semiconducting diamond nanoparticles. Evidence for moderate doping levels in some particles (~1017 B cm−3), is found alongside the observation that some particles are heavily doped (~1020 B cm−3) and likely to be quasi-metallic in character. The current study has therefore shown that substitutional boron doping in nm NDs is in fact possible, opening-up the path to a whole host of new applications for this interesting class of nano-particles.